U.S. patent number 5,057,572 [Application Number 07/424,244] was granted by the patent office on 1991-10-15 for aqueous, finely divided to optically clear, thermally and mechanically stable silicone emulsions, a process for their preparation and their use.
This patent grant is currently assigned to Ciba-Geigy Corporation. Invention is credited to Harald Chrobaczek, Gunther Tschida.
United States Patent |
5,057,572 |
Chrobaczek , et al. |
October 15, 1991 |
Aqueous, finely divided to optically clear, thermally and
mechanically stable silicone emulsions, a process for their
preparation and their use
Abstract
The present invention describes aqueous, finely divided to
optically clear, thermally and mechanically stable silicone
emulsions, these emulsions containing, relative to the overall
emulsions 3 to 25% by weight of a water-soluble emulsifier (a), 0.1
to 84% by weight of an aminoalkyl-substituted polysiloxane (b)
(amine number 0.1), in which, if appropriate, is present, at least
partially, in salt form, and up to 70% by weight of which may be
replaced by other polysiloxanes (emulsifier:silicone ratio at least
1.2:10), up to 3% by weight of a low-molecular weight, weak acid
(c) and at least 5% by weight of water, (d), the sum of a), b), c)
and d) being 100% by weight. In addition, a process is also
patented for the preparation and use of these emulsions. The
silicone emulsions according to the invention are distinguished by
excellent thermal stability.
Inventors: |
Chrobaczek; Harald (Augsburg,
DE), Tschida; Gunther (Schwabmunchen, DE) |
Assignee: |
Ciba-Geigy Corporation
(Ardsley, NY)
|
Family
ID: |
25854937 |
Appl.
No.: |
07/424,244 |
Filed: |
October 16, 1989 |
PCT
Filed: |
April 07, 1988 |
PCT No.: |
PCT/EP88/00285 |
371
Date: |
October 16, 1989 |
102(e)
Date: |
October 16, 1989 |
PCT
Pub. No.: |
WO88/08436 |
PCT
Pub. Date: |
November 03, 1988 |
Foreign Application Priority Data
|
|
|
|
|
Apr 24, 1987 [DE] |
|
|
3713789 |
Jul 17, 1987 [DE] |
|
|
3723697 |
|
Current U.S.
Class: |
524/588; 8/116.1;
428/391; 442/102 |
Current CPC
Class: |
C08J
3/03 (20130101); D06M 15/6436 (20130101); C08J
2383/04 (20130101); Y10T 428/2962 (20150115); Y10T
442/2352 (20150401) |
Current International
Class: |
C08J
3/03 (20060101); C08J 3/02 (20060101); D06M
15/643 (20060101); D06M 15/37 (20060101); C08K
005/06 (); D06M 015/643 () |
Field of
Search: |
;524/588
;428/391,266 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Hoke; Veronica P.
Attorney, Agent or Firm: Dohmann; George R. McC. Roberts;
Edward
Claims
I claim:
1. A process for preparing an aqueous, finely divided to optically
clear, thermally and mechanically stable silicone emulsion
containing
(a) 3 to 25 parts by weight of an emulsifier which is soluble in
water,
(b) 0.1 to 84 parts by weight of polysiloxane said polysiloxane
consisting of 30 to 100 percent by weight of aminoalkyl-substituted
polysiloxane having an amine number of at least 0.1, and 0 to 70
percent by weight of amino-free polysiloxane,
(c) 0.05 to 3.05 parts by weight of an acid,
(d) 5 to 96.85 parts by weight of water,
with the proviso that the parts of the emulsifier, the
polysiloxane, the acid and the water add up to 100 parts by weight
of the emulsion and with the further proviso that the ratio of (a)
and (b) is at least 1.2:10;
said process comprising the steps of warming to at least 50.degree.
C., with stirring a mixture, containing at least the emulsifier,
(a), and the water, (d), but which may also contain either the
polysiloxane, (b), or both of (b) and the acid, (c), and
establishing a pH of from 3 to 7 until a homogeneous phase is
formed, with the proviso that if (b) and (c) or only (c) are not
present in the mixture prior to warming, said process further
comprises adding the missing components selected from (b) and (c)
to the warm mixture, such that the mixture contains all four of
(a), (b), (c), and (d).
2. A process of claim 1 wherein the emulsion contains 8 to 12 parts
by weight of (a) and 0.3 to 0.7 parts by weight of (c).
3. A process of claim 1 wherein a mixture of (a), (b) and (d) is
warmed and then (c) is added.
4. A process of claim 1 wherein a mixture of (a) and (d) is warmed
and then (b) and (c) are added.
5. A process of one of claims 1 or 2 wherein the emulsion contains
5 to 70 parts by weight of (b).
6. A process of claim 5 wherein the emulsion contains 12 to 18
parts by weight of (b).
7. A process of claim 1 wherein (a) is selected from the group
consisting of primary or secondary, linear or branched C.sub.8
-C.sub.16 -alkyl polyglycol ethers and C.sub.6 -C.sub.12
-alkylphenol ethoxylates.
8. A process of claim 1 wherein (b) contains 0 percent by weight of
the amino-free polysiloxane.
9. A process of claim 1 wherein the mixture is warmed to a
temperature of from 50.degree. C. to 120.degree. C.
10. A process of claim 9 wherein the mixture is warmed to a
temperature of from 60.degree. C. to 95.degree. C.
11. A process of claim 1 wherein the finished emulsion has a pH of
from 5.0 to 7.0.
12. A process of claim 5 wherein (a) is selected from the group
consisting of primary or secondary, linear or branched C.sub.8
-C.sub.16 -alkyl polyglycol ethers and C.sub.6 -C.sub.12
-alkylphenylalkoxylates and the mixture is warmed to a temperature
of from 50.degree. to 120.degree. C.
13. An aqueous, finely divided to optically clear, thermally and
mechanically stable silicone emulsion containing
(a) 3 to 25 parts by weight of an emulsifier which is soluble in
water,
(b) 0.1 to 84 parts by weight of polysiloxane said polysiloxane
consisting of 30 to 100 percent by weight of aminoalkyl-substituted
polysiloxane having an amine number of at least 0.1, and 0 to 70
percent by weight of amino-free polysiloxane,
(c) 0.05 to 3.05 parts by weight of an acid,
(d) 5 to 96.85 parts by weight of water,
with the proviso that the parts of the emulsifier, the
polysiloxane, the acid and the water add up to 100 parts by weight
of the emulsion and with the further proviso that the ratio of (a)
and (b) is at least 1.2:10.
14. An emulsion of claim 13 which contains 8 to 12 parts by weight
of (a), 5 to 70 parts by weight of (b) and 0.3 to 0.7 parts by
weight of (c).
15. An emulsion of claim 14 which contains 12 to 18 parts by weight
of (b).
16. An emulsion of claim 14 wherein (a) is selected from the group
consisting of primary or secondary, linear or branched C.sub.8
-C.sub.16 -alkyl polyglycol ethers and C.sub.6 -C.sub.12
-alkylphenol ethoxylates.
17. A method of finishing textiles which comprises treating a
textile with an aqueous, finely divided to optically clear,
thermally and mechanically stable silicone emulsion containing
(a) 3 to 25 parts by weight of an emulsifier which is soluble in
water,
(b) 0.1 to 84 parts by weight of polysiloxane said polysiloxane
consisting of 30 to 100 percent by weight of aminoalkyl-substituted
polysiloxane having an amine number of at least 0.1, and 0 to 70
percent by weight of amino-free polysiloxane,
(c) 0.05 to 3.05 parts by weight of an acid,
(d) 5 to 96.85 parts by weight of water,
with the proviso that the parts of the emulsifier, the
polysiloxane, the acid and the water add up to 100 parts by weight
of the emulsion and with the further proviso that the ratio of (a)
and (b) is at least 1.2:10.
18. A method of claim 17 wherein the emulsion contains further
known textile auxiliaries selected from the group consisting of
biocides, anti-static agents, stiffening agents, synthetic resins,
oilproofing agents, waterproofing agents and attendant
catalysts.
19. A process of claim 1 wherein the acid, (c), is a
low-molecular-weight organic acid.
Description
The present invention describes aqueous, finely divided to
optically clear, thermally and mechanically stable silicone
emulsions based on aminoalkyl-substituted polysiloxanes, the
preparation of these emulsions, and their use.
The preparation of silicone emulsions with high-pressure
emulsification has long been known (German Patent 1,060,347, U.S.
Pat. Nos. 3,320,197 and 3,748,275). In addition, the preparation of
polyorganosiloxane microemulsions is known from EP-OS 138,192. In
this case, the starting substances, namely the polyorganosiloxane
containing a polar radical and the surfactant, are mixed and added
to water in order to form a translucent oil concentrate, and the
concentrate obtained is then rapidly dispersed in water. This
preparation of microemulsions presents considerable problems with
respect to type conformity, but above all, the emulsions obtained
only have an unsatisfactory thermal stability.
It has now been found that, when very certain starting compounds in
selected mixing ratios are used without high-pressure
homogenization, aqueous, finely divided to optically clear silicone
emulsions are produced which are thermally and mechanically stable
under the customary conditions and, in addition, can be prepared in
a surprisingly simple fashion by stirring together silicone
emulsifier and water, warming and adding acid.
Accordingly, the present invention describes, in Patent Claims 1 to
5, aqueous, finely divided to optically clear, thermally stable
silicone emulsions. A process for the preparation of these silicone
emulsions is patented in Patent Claims 6 to 10 and their use is
patented in Patent Claim 11.
The compounds a) used are emulsifiers which are soluble in water to
form a clear to transparent solution (called "water-soluble"
below), in particular nitrogen-free emulsifiers. These emulsifiers
are known, and those skilled in the art will have no problem in
selecting the correct products. Examples which may be
mentioned--without claiming comprehensiveness--are the following
emulsifiers: ethylene oxide adducts of fatty alcohols, in
particular those of primary and/or secondary linear to branched
alcohols having 8 to 16 C atoms and ethoxylated C.sub.6-12
-alkylphenols, it being necessary to select the number of ethylene
oxide units so that water solubility is produced. Compounds which
are preferably used are
2,6,8-trimethyl-4-nonyloxyhexapolyethyleneoxyethanol, isotridecyl
ethoxylate having an average of 8 ethylene oxide units, ethoxylated
secondary dodecyl alcohol or n-decyl alcohol having an average of
12 moles of ethylene oxide, and nonylphenol polyglycol ether having
an average of 10 ethylene oxide units. However, highly suitable
emulsifiers are, in addition, also silicone surfactants as are
produced by ethoxylation and/or propoxylation of polysiloxanes, so
long as water solubility is ensured. The alkoxylation can take
place as a side chain or terminally, and the chain length depends
on the number of -[Si(CH.sub.3).sub.2 O].sub.n. Thus, for example,
in polysiloxanes where n=1 to 5, 6 to 8 ethylene oxide units on
average are present in the molecule, for example the following
silicone surfactant: ##STR1##
Compounds b) are aminoalkyl-substituted polysiloxanes having an
amine number of at least 0.1, in particular at least 0.3, those
polysiloxanes which have an amine number of 0.3 to 1.0 being very
particularly preferably employed. The amine number here is defined
as the consumption of 1N hydrochloric acid in millilitres per 1 g
of substance (=sample weight). The compounds b) here may also be
present, at least partially, in the form of salts with the
compounds c).
The positioning of the aminoalkyl groups may be terminal and as a
side chain. The aminoalkyl groups generally have the formula
--RNHR.sup.1 where R represents a divalent hydrocarbon radical
having 2 to 8, in particular 3 or 4 C atoms and R.sup.1 =hydrogen,
an alkyl radical having 1 to 4 C atoms or the --CH.sub.2 CH.sub.2
NH.sub.2 radical. The amino-functional radical preferably has the
following structure: --CH.sub.2 CH.sub.2 CH.sub.2 --NH--CH.sub.2
--CH.sub.2 --NH.sub.2 or --CH.sub.2 --CH(CH.sub.3)CH.sub.2
--NH--CH.sub.2 --CH.sub.2 --NH.sub.2.
In addition to the aminoalkyl groups which are necessarily present,
there are no particular limitations with respect to the structure
of the polysiloxanes which can be used. Thus, it is possible to use
straight-chain and/or branched polysiloxanes, in particular
dimethyl polysiloxanes, which are substituted by aminoalkyl groups
and which also contain terminal OH groups or side-chain hydrocarbon
or substituted hydrocarbon radicals, in particular vinyl and/or
phenyl radicals. From this description, it is easy to see that
compounds b) which can be employed without hesitation are also
obtained by further modification of aminoalkyl-substituted
polysiloxanes, so long as the minimum amine number required is
ensured by choice of the reaction ratio. The amino-functional
polysiloxanes which can be employed are generally known and
therefore require no further explanation.
The compounds c) are also known to those skilled in the art.
Examples of acids which may be mentioned are hypophosphorous acid,
nitric acid and hydrochloric acid, but in particular low-molecular
weight organic acids such as lactic acid, glycolic acid, propionic
acid, formic acid and, above all, for economic reasons, acetic
acid.
The compounds d) are normal tap water. However, it is also possible
to use distilled or demineralized water, it being advantageous
here, in the case of relatively high concentrations of compound b),
to convert to continuous preparation of the finished emulsions
since somewhat more finely divided emulsions result by this
method.
The decisive factors in the silicone emulsions according to the
invention are not only the compounds employed, but also, above all,
the mixing ratios of the individual compounds to one another. Thus,
it is absolutely necessary that the thermally and mechanically
stable silicone emulsions according to the invention contain 3 to
25% by weight of compound a), 0.1 to 84% by weight of compound b),
up to 3% by weight of compound c) and at least 5% by weight of
water, in each case relative to the overall emulsion, since the
silicone emulsions desired are only produced if these mixing ratios
are adhered to with spontaneous emulsification. Particular
reliability is ensured here if the silicone emulsion contains 8 to
12% by weight of compound a), up to 1% by weight of compound c) and
5 to 70% by weight of compound d), compound d) usually being
customary tap water. The sum of compounds a), b) and d) is, of
course, 100% by weight.
However, in order to produce the silicone emulsions desired, it is,
in addition, absolutely necessary to ensure that the
emulsifier:silicone ratio (the term silicone here is taken to mean
both compounds b) and the sum of compounds b) and e, compound e)
being defined below)) is at least 1.2:10.
If the object is the preparation of oil-in-water emulsions, the
amount of compound b) should be limited to a maximum of 70% by
weight, above all 5 to 70% by weight.
Optically clear silicone emulsions (microemulsions) according to
the invention are very particularly preferred. These emulsions
contain up to 70% by weight, in particular up to 18% by weight,
particularly preferably 12to 18% by weight, of compounds b). The
amount of acid in these optically clear silicone emulsions is
particularly crucial. The customary emulsions containing 15 to 40%
of compound b) (such emulsions are no longer obtained using
compounds e)) contain up to 0.6% by weight, in particular 0.25 to
0.6% by weight of pure 100% acid, but the amounts may increase
slightly (up to about 1% by weight) in the case of more highly
concentrated silicone emulsions.
Surprisingly, very finely divided silicone emulsions are also
present if up to 70% by weight of compound b) are replaced by other
amino group-free polysiloxanes (compound e)). Suitable compounds e)
here are more or less all polysiloxanes having another
functionality. Examples which may be mentioned are:
.alpha.,.omega.-diepoxy-,.alpha.,.omega.-dialkoxydimethylpolysiloxane,
dimethylpolysiloxane having a vinyl, acrylate and phenoxyalkyl
functionality, but also .alpha.,.omega.-dicarbinol and
amide-functional organopoly-siloxanes. These silicone emulsions are
less thermally stable (up to about 70.degree. C.) compared to
emulsions of compounds b) alone.
In order to prepare the silicone emulsions, the compounds a), b)
and d) are initially introduced and warmed to at least 50.degree.
C. with stirring. However, it is also possible to initially
introduce only compounds a) and d), to warm the mixture and only
then to add compound b) with stirring, compound b) preferably
always being employed in salt-free form and it being possible to
replace up to 70% by weight of compound b) by compound e). The
upper limit for the temperature is set only by the increase in
pressure, and the mixture is preferably not warmed to more than
120.degree. C., it naturally being necessary in this case to work
in a sealed system. A temperature range from 60.degree. to
95.degree. C. is particularly favourable since the overall
preparation proceeds sufficiently quickly in this range and it is
possible to work without the use of pressure. Uniform distribution
requires only a relatively short time, generally 1 to 10 minutes,
usually only 1 to 5 minutes being entirely sufficient. As soon as a
uniform mixture has been produced, compound c) is stirred in at the
working temperature, which causes a homogeneous phase to form
temporarily, i.e. the silicone emulsion desired has formed with
spontaneous emulsification. A pH of 3.0 to 7.0, in particular 5.0
to 7.0 is produced by adding compound c). Taking into account the
simultaneous salt formation of compounds b), the amounts which are
necessary for this purpose are 0.05 to 3.05, in particular 0.1 to
1.1 and, in order to produce true microemulsions, particularly
preferably 0.3 to 0.7 parts by weight of compound c) (relative to
100% acid). The amounts of compounds a), b) and d) are,
corresponding to the amounts of the finished silicone emulsions, 3
to 25, in particular 8 to 12, parts by weight of compound a), 0.1
to 84, in particular 5 to 70, particularly preferably 12 to 18,
parts by weight of compound b), and 5 to 96.85, above all 5 to 70,
in particular 21.1 to 91.8, particularly preferably 57 to 79.9,
parts by weight of compound d), the sum of compounds a), b) and d)
and the amount of compound c) used for the pH adjustment being 100
parts by weight.
However it is also possible to introduce the entire amount of
compound c) from the beginning, i.e. to include compound b) in salt
form for the preparation of the emulsions. This procedure is
likewise possible without hesitation, but a longer period of time
is required in this case in order to achieve spontaneous
emulsification at the elevated temperature.
For stability reasons, it should be ensured that, where necessary,
acid is added after the preparation so that it remains guaranteed
that the pH does not exceed 7 during storage. For stability
reasons, the addition of a customary commercial biocide may also be
entirely advantageous. In both cases, the addition should take
place at below 40.degree. C.
It could not have been expected from the prior art that finely
divided to optically clear silicone emulsions are obtained using
the compounds selected in the mixing ratios selected under the
process conditions described with spontaneous emulsification, it
being particularly surprising that water-clear silicone emulsions
can be prepared, even at high concentration in such a simple
manner. These emulsions have excellent transparency and are just as
thermally stable as the finely divided silicone emulsions.
Transparency here can be determined in a simple manner using a
Lange turbidity photometer LTP 5, the turbidity units in accordance
with the formazine standard (TU/S) permitting an expression of the
emulsion quality (value for water about 0.25). However, the fact
that the emulsions according to the invention, so long as they are
optically clear, have a very high thermal stability, a property
which has hitherto not been satisfactorily obtained by the prior
art, is important and crucial here. Even if finely divided
emulsions are produced, however, the latter are still very highly
thermally stable (up to at least 70.degree. C.). In addition, the
emulsions prepared according to the invention also have a high
mechanical stability, above all toward shaking and shear
forces.
The silicone emulsions according to the invention (for processing
reasons the latter are usually adjusted to 15 to 40% by weight of
silicone) can be used as such for textile finishing by customary
methods, namely, in particular, by the exhaust and pad-mangle
methods. However, it is also possible here to simply combine these
emulsions with other known textile auxiliaries--even when warm
during preparation--the handle, in particular, being favourably
influenced by the agents according to the invention. The textiles
thus treated in a customary manner may be distinguished by a
particularly smooth-surfaced, flowing soft handle.
Suitable such additives are commercially available antistatic
agents, stiffening agents, synthetic resins, oilproofing and
waterproofing agents and attendant catalysts.
The invention is now illustrated in greater detail with reference
to the Examples below, parts denoting parts by weight and %
denoting % by weight.
EXAMPLES 1 to 4
The compounds a), b) and d) mentioned below are mixed with one
another as stated, warmed to 80.degree. C. and distributed
uniformly within 2 to 3 minutes by stirring at this temperature.
The stated amount of acetic acid is subsequently added at the
temperature mentioned and spontaneous emulsification takes place
immediately, i.e. the mixtures immediately become clear. The
mixture is then allowed to cool to room temperature. In order to
determine the turbidity, the microemulsions obtained are
subsequently measured without solvent using a Lange turbidity
photometer.
The amounts specified are parts by weight.
______________________________________ Example Example Example
Example 1 2 3 4 ______________________________________ Water
(compound d) 74.6 74.6 74.6 74.6 Compound a1) 10 10 Compound a2) 10
Compound a3) 10 Compound b1) 15 Compound b2) 15 Compound b3) 15
Compound b4) 15 Glacial acetic 0.4 0.4 0.4 0.4 acid pH 5.5 5.5 5.5
5.5 TU/F 6 6 8 50 (Turbidity units, formazine) Appearance water-
water- water- very clear clear clear slightly bluish Thermal + + +
+ stability (tested at 95.degree. C. for 2 hours)
______________________________________ + = thermally stable - =
thermally unstable a1) = C.sub.11-15 sec. alcohol ethoxylate having
an average of 7 ethylene oxide units, a2) =
2,6,8trimethyl-4-nonyloxypolyethyleneoxyethanol, ( .RTM.TERGITOL
TMN6 from Union Carbide Europe SA), a3) = Isotridecyl ethoxylate
with an average of 8 ethylene oxide units, b1) = linear,
trimethylsilylterminated dimethylpolysiloxane having
(CH.sub.2).sub.34NHCH.sub.2CH.sub.2NH.sub.2 side chains (viscosity
about 1000 mPa .multidot. s at 20.degree. C.; amine number 0.62),
b2) = linear OHterminated dimethylpolysiloxane having
(CH.sub.2).sub.3NHCH.sub.2NH.sub.2 side chains (viscosity about
1900 mPa .multidot. s at 20.degree. C.; amine number 0.58) ##STR2##
R =(CH.sub.2).sub.3NHCH.sub.2CH.sub.2NH.sub.2 and b4) = branched,
OHterminated dimethylpolysiloxane having
(CH.sub.2).sub.3NHCH.sub.2CH.sub.2NH.sub.2 side and terminal chains
(viscosity about 1050 mPa .multidot. s at 20.degree. C.; amine
number 0.3).
If the same procedure as in Example 1 is carried out using 0.4
parts of concentrated nitric acid, a bluish emulsion is obtained
(TU/F 80).
EXAMPLE 5
If Example 1 is repeated using the same amount of the silicone
surfactant mentioned in the discussion of the emulsifiers, a
slightly bluish, thermally extremely stable microemulsion is
obtained which is insensitive towards shear stress.
EXAMPLE 6
While warming at 70.degree. C., 8 parts of the compound a2)
described in Example 1 are stirred with 16 parts of an
amino-functional polysiloxane (linear, OH-terminated
dimethylpolysiloxane having --(CH.sub.2).sub.3 --NH--CH.sub.2
--CH.sub.2 --NH.sub.2 side chains; viscosity about 5000 to 6000
mPa.s at 20.degree. C.; amine number 0.12) and 74 parts of water to
form a homogeneous mixture. 1 part of lactic acid is subsequently
added at the temperature mentioned and the microemulsion is
produced spontaneously and becomes clear. After cooling, a clear,
thermally extremely stable emulsion which is very highly suitable
for softening textiles is obtained.
EXAMPLE 7
Example 2 is repeated using 20 parts of nonylphenol polyglycol
ether (containing 9 ethylene oxide units per mole of nonylphenol)
and 64 parts of water. A likewise water-clear microemulsion is
obtained which is both cold-stable and very heat-stable and
exhibits no change even after shaking for 2 hours.
EXAMPLE 8
Example 1 is repeated by adding at the beginning 0.05 part of
glacial acetic acid to compound b1) and proceeding as described
therein. An equally good emulsion is obtained after addition of the
remaining glacial acetic acid and stirring briefly.
EXAMPLE 9
Example 1 is repeated at 95.degree. C. (stirring time 5 to 6
minutes) using 25 parts of the following aminoalkyl-substituted
polysiloxane and a correspondingly reduced amount of water: a
highly branched, trimethyl-terminated dimethylpolysiloxane (amine
number about 0.6; viscosity about 1200 mPa.s at 20.degree. C.).
EXAMPLES 10 to 14
Compounds a), b), d) and e) mentioned below are mixed in the manner
specified, warmed to 70.degree. to 80.degree. C. by stirring at
this temperature for a few minutes (2 to 6 minutes depending on the
viscosity of compounds b) and e) and uniformly distributed. The
finished emulsion is subsequently prepared spontaneously by adding
compound c). The emulsion is then allowed to cool to room
temperature.
______________________________________ Examples: 10 11 12 13 14
______________________________________ Water 48.4 9 64.6 34.8 52.7
Compound d) Compound a1) -- 10 10 -- -- Compound a2) -- -- -- 10 10
Compound a4) 10 -- -- -- -- Compound b1) 40 -- 15 25 12 Compound
b5) -- 80 -- -- -- Glacial -- -- 0.4 0.2 0.3 acetic acid Conc.
hydro- 1.6 -- -- -- -- chloric acid 57% strength -- 1 -- -- --
glycolic acid (= compounds c) Compound e1) -- -- -- -- 25 Compound
e2) -- -- -- 30 -- Compound e3) -- -- 10 -- -- pH 6.6 6.7 6.5 6.8
6.6 Appearance water water finely finely finely clear clear divided
divided divided Thermal + + + + + stability (2 hours at 60.degree.
C.) ______________________________________ a4) = ndodecyl
ethoxylate having an average of 6 ethylene oxide units b5) = as the
polysiloxane described in Example 6 having a viscosity of about 750
mPa .multidot. s at 20.degree. C. and an amine number of about 0.6
##STR3## ##STR4## Viscosity about 40 mPa .multidot. s at 20.degree.
C.; iodine number about 66. e3) Strucutre as for e2) having a
##STR5## side chain in place of the vinyl group Viscosity about 50
mPa .multidot. s at 20.degree. C.; epoxy number about 0.2.
EXAMPLE 15
72.91 parts of demineralized water,
6.66 parts of emulsifier (see Example 2, compound a3),
20.00 parts of an amino-functional polysiloxane (branched),
OH-terminated dimethylpolysiloxane; viscosity about 1050 mPa.s at
20.degree. C.; amine number 0.30) and
0.43 part of 60% strength acetic acid
are warmed to about 80.degree. C. while stirring. After about 30
minutes at this temperature, the microemulsion has been produced
while slowly becoming clear. The emulsion is now stirred until
cold. A thermally stable silicone emulsion is produced.
USE EXAMPLE 1
a) Pad-mangle method
The knitted cotton fabric (200 g/m.sup.2) is pad-mangled with a
liquor containing 30 g/l of the emulsion prepared according to
Example 1 (liquor pH 5.5), squeezed out to a liquor take-up of
about 90% and dried for 10 minutes at 110.degree. C.
An extremely smooth-surfaced, specifically soft, flowing handle
results, the fabric additionally being distinguished by high
springiness and a considerable increase in the crease recovery
properties.
b) Exhaust method
The microemulsion described in Example 1 is used to finish the same
knitted cotton fabric by dipping the latter into a working liquor
(liquor ratio 1:20), left therein for 20 minutes at 20.degree. C.
and then dried as described above. In this way 0.4% by weight of
active substance is applied to the fabric by about 85% exhaustion
of the liquor. Corresponding finishing effects are obtained.
USE EXAMPLE 2
In order to complete the effect, 10 to 30 g of each of the finishes
mentioned below can be added to the emulsion of Example 12:
(1) about 70% strength aqueous solution of
dimethyloldihydroxyethyleneurea which has been etherified using
methanol,
(2) about 42% strength non-ionogenic polyvinyl acetate dispersion,
or
(3) about 52% strength non-ionogenic hydrogen methyl polysiloxane
dispersion.
Customary textile materials, for example also cotton poplin,
cotton/synthetic mixed fabric or regenerated cellulose, can be
provided with excellent overall properties in a known fashion,
using these combination products.
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